摘要
以6-311+g(3df)为基组,采用B3PW91方法研究了PO2自由基在不同外电场(-0.05~0.05 a.u.)下的基态参数、总能量、偶极矩、电荷分布、HOMO能级、LUMO能级和能隙,在优化构型的基础上,使用相同的基组和同等强度的外电场,采用CIS-DFT方法研究了PO2自由基前9个激发态的激发能、跃迁波长和振子强度.结果表明:PO2的几何参数随电场强度大小及方向变化明显.电场由-0.05 a.u.变化至0.05 a.u.时,体系的总能量先减少后增加,偶极矩不断减少,HOMO能级、LUMO能级和能隙随电场的变化明显.激发态的激发能和波长与外电场有强烈的依赖关系,而振子强度随外电场变化微小.
A density functional method(B3PW91)with 6-311+G(3df)basis sets has been used to study the equilibrium geometric parameters,total energies,dipole moments,charge distributions,the highest occupied molecular orbital(HOMO)energies,the lowest unoccupied molecular orbital(LUMO)energies,energy gaps of PO2 radical under different external electric field ranging from-0.05 to 0.05 a.u.On the basis of optimized configuration,the excitation energy,transition wavelength and oscillator strength in the same intense external electric field and basis sets are calculated by the configuration interaction singles(CIS-B3PW91)method.The results show that the geometric parameters of PO2 radical strongly depend on the magnitude and direction of external electric field.The total energy of PO2 radical in different external electric fields ranging from-0.05 to 0.05 a.u.first decreases and then increases,the dipole moments of PO2 radical decrease;The change of the HOMO energy、LUMO energy and the energy gaps of PO2 radical is obvious with the electric field.The excitation energy and wavelength of the excited state are strongly dependent on the external electric field,while the oscillator strength changes little with the external electric field.
作者
荆涛
梁冬梅
孙光宇
JING Tao;LIANG Dongmei;SUN Guangyu(KaiLi University,KaiLi,Guizhou,556011,China;Guizhou Normal University,Guiyang,Guizhou,550018,China)
出处
《凯里学院学报》
2020年第6期14-19,共6页
Journal of Kaili University
基金
国家自然科学基金资助项目(11764024)
贵州省教育厅科技拔尖人才项目(黔教合KY字[2017])
贵州省教育厅青年科技人才成长项目(黔教合KY字[2019]185)。
关键词
外电场
激发态
振子强度
External electric field
excited states
oscillator strength
